CN116751150A - 一种2位吲哚基取代吲哚-3-酮类化合物的合成方法 - Google Patents
一种2位吲哚基取代吲哚-3-酮类化合物的合成方法 Download PDFInfo
- Publication number
- CN116751150A CN116751150A CN202310682289.9A CN202310682289A CN116751150A CN 116751150 A CN116751150 A CN 116751150A CN 202310682289 A CN202310682289 A CN 202310682289A CN 116751150 A CN116751150 A CN 116751150A
- Authority
- CN
- China
- Prior art keywords
- indole
- indolyl
- indol
- equiv
- synthesizing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 2-indolyl Chemical group 0.000 title claims abstract description 28
- 238000001308 synthesis method Methods 0.000 title claims description 10
- 239000000758 substrate Substances 0.000 claims abstract description 28
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims abstract description 23
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims abstract description 13
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 8
- 239000002841 Lewis acid Substances 0.000 claims abstract description 7
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 7
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 18
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 6
- 150000005626 indol-3-ones Chemical class 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- HZXJVDYQRYYYOR-UHFFFAOYSA-K scandium(iii) trifluoromethanesulfonate Chemical compound [Sc+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HZXJVDYQRYYYOR-UHFFFAOYSA-K 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000005580 one pot reaction Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 claims description 2
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 claims description 2
- 150000002504 iridium compounds Chemical class 0.000 claims description 2
- PGJLOGNVZGRMGX-UHFFFAOYSA-L iron(2+);trifluoromethanesulfonate Chemical compound [Fe+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F PGJLOGNVZGRMGX-UHFFFAOYSA-L 0.000 claims description 2
- KVRSDIJOUNNFMZ-UHFFFAOYSA-L nickel(2+);trifluoromethanesulfonate Chemical compound [Ni+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F KVRSDIJOUNNFMZ-UHFFFAOYSA-L 0.000 claims description 2
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 claims description 2
- 150000003304 ruthenium compounds Chemical class 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 2
- JPJIEXKLJOWQQK-UHFFFAOYSA-K trifluoromethanesulfonate;yttrium(3+) Chemical compound [Y+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F JPJIEXKLJOWQQK-UHFFFAOYSA-K 0.000 claims description 2
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 2
- 239000000975 dye Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 38
- 230000015572 biosynthetic process Effects 0.000 abstract description 21
- 238000003786 synthesis reaction Methods 0.000 abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 abstract description 19
- 239000001301 oxygen Substances 0.000 abstract description 19
- 125000001041 indolyl group Chemical group 0.000 abstract description 5
- 238000010189 synthetic method Methods 0.000 abstract 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 50
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 48
- 238000005481 NMR spectroscopy Methods 0.000 description 48
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 32
- KLLLJCACIRKBDT-UHFFFAOYSA-N 2-phenyl-1H-indole Chemical compound N1C2=CC=CC=C2C=C1C1=CC=CC=C1 KLLLJCACIRKBDT-UHFFFAOYSA-N 0.000 description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- 239000012298 atmosphere Substances 0.000 description 17
- 238000001228 spectrum Methods 0.000 description 17
- 238000002844 melting Methods 0.000 description 16
- 230000008018 melting Effects 0.000 description 16
- 239000003208 petroleum Substances 0.000 description 16
- BHNHHSOHWZKFOX-UHFFFAOYSA-N 2-methyl-1H-indole Chemical compound C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 description 15
- WHELTKFSBJNBMQ-UHFFFAOYSA-L dichlororuthenium;2-pyridin-2-ylpyridine;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ru+2].N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 WHELTKFSBJNBMQ-UHFFFAOYSA-L 0.000 description 15
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 239000007858 starting material Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- 238000000926 separation method Methods 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 7
- YHYLDEVWYOFIJK-UHFFFAOYSA-N 1h-indole-5-carbonitrile Chemical compound N#CC1=CC=C2NC=CC2=C1 YHYLDEVWYOFIJK-UHFFFAOYSA-N 0.000 description 4
- ODFFPRGJZRXNHZ-UHFFFAOYSA-N 5-fluoroindole Chemical compound FC1=CC=C2NC=CC2=C1 ODFFPRGJZRXNHZ-UHFFFAOYSA-N 0.000 description 4
- DWAQDRSOVMLGRQ-UHFFFAOYSA-N 5-methoxyindole Chemical compound COC1=CC=C2NC=CC2=C1 DWAQDRSOVMLGRQ-UHFFFAOYSA-N 0.000 description 4
- YTYIMDRWPTUAHP-UHFFFAOYSA-N 6-Chloroindole Chemical compound ClC1=CC=C2C=CNC2=C1 YTYIMDRWPTUAHP-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- IENZCGNHSIMFJE-UHFFFAOYSA-N indole-5-carboxylic acid Chemical compound OC(=O)C1=CC=C2NC=CC2=C1 IENZCGNHSIMFJE-UHFFFAOYSA-N 0.000 description 4
- FSWVIWIAKATFQG-UHFFFAOYSA-N 2-ethyl-2-(1h-indol-3-yl)-1h-indol-3-one Chemical compound C1=CC=C2C(C3(C(C4=CC=CC=C4N3)=O)CC)=CNC2=C1 FSWVIWIAKATFQG-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- SICXSECDUCIVAU-UHFFFAOYSA-N 2-(1H-indol-3-yl)-2-methyl-1H-indol-3-one Chemical compound C1=CC=C2C(C3(C(C4=CC=CC=C4N3)=O)C)=CNC2=C1 SICXSECDUCIVAU-UHFFFAOYSA-N 0.000 description 2
- UDLWYQHLXQLPSK-UHFFFAOYSA-N 2-(hydroxymethyl)-2-(2-oxo-1,3-dihydroindol-3-yl)-1H-indol-3-one Chemical compound O=C1NC2=CC=CC=C2C1C1(CO)C(=O)C2=CC=CC=C2N1 UDLWYQHLXQLPSK-UHFFFAOYSA-N 0.000 description 2
- BWNBLGQCCSCCHF-UHFFFAOYSA-N 2-ethyl-1h-indole Chemical compound C1=CC=C2NC(CC)=CC2=C1 BWNBLGQCCSCCHF-UHFFFAOYSA-N 0.000 description 2
- VXWVFZFZYXOBTA-UHFFFAOYSA-N 5-bromo-1h-indole Chemical compound BrC1=CC=C2NC=CC2=C1 VXWVFZFZYXOBTA-UHFFFAOYSA-N 0.000 description 2
- MYTGFBZJLDLWQG-UHFFFAOYSA-N 5-chloro-1h-indole Chemical compound ClC1=CC=C2NC=CC2=C1 MYTGFBZJLDLWQG-UHFFFAOYSA-N 0.000 description 2
- MFZQJIKENSPRSJ-UHFFFAOYSA-N 5-chloro-1h-pyrrolo[2,3-b]pyridine Chemical compound ClC1=CN=C2NC=CC2=C1 MFZQJIKENSPRSJ-UHFFFAOYSA-N 0.000 description 2
- WZAXFWPPRZFJNA-UHFFFAOYSA-N N1C=C(C2=CC=CC=C12)C1(NC2=CC=CC=C2C1=O)C1=CC=CC=C1 Chemical compound N1C=C(C2=CC=CC=C12)C1(NC2=CC=CC=C2C1=O)C1=CC=CC=C1 WZAXFWPPRZFJNA-UHFFFAOYSA-N 0.000 description 2
- 229930013930 alkaloid Natural products 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006880 cross-coupling reaction Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- DRYBMFJLYYEOBZ-UHFFFAOYSA-N methyl 1h-indole-5-carboxylate Chemical compound COC(=O)C1=CC=C2NC=CC2=C1 DRYBMFJLYYEOBZ-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000036436 anti-hiv Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007876 drug discovery Methods 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004095 oxindolyl group Chemical group N1(C(CC2=CC=CC=C12)=O)* 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
- C07D209/32—Oxygen atoms
- C07D209/36—Oxygen atoms in position 3, e.g. adrenochrome
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
Abstract
本发明公开一种2位吲哚基取代吲哚‑3‑酮类化合物的合成方法,涉及一种绿色、温和、高效且操作简单的合成2位吲哚基取代吲哚‑3‑酮化合物的方法。本方法以2‑取代吲哚和吲哚为原料,在可见光光敏剂、路易斯酸以及氧气存在下,通过可见光照射能在室温条件下经一步分子间反应制得2位吲哚基取代的吲哚‑3‑酮化合物。该方法利用清洁的光能,具有反应条件温和,操作简单,合成步骤简短,反应底物普适性好以及反应收率高等优点。
Description
技术领域
本发明涉及一种2位吲哚基取代吲哚-3-酮类化合物及其合成方法,属于有机化合物合成技术领域。
背景技术
吲哚-3-酮是一种广泛存在于天然产物和生物活性分子中的独特的含氧吲哚结构,同时也是合成其他活性生物碱和小分子化合物所需的重要前体。例如生物碱Halichrome A,Cephaninone C,Isatisine A,trigonoliimine C。
近年来,吲哚-3-酮类化合物被发现具有抗癌、抗肿瘤、抗HIV、抗病毒感染、抗菌等生物活性,可作为药物发现的重要源泉。因此,研究并开发该类化合物的温和、高效合成方法不仅具有重要的理论意义,而且具有潜在的应用价值。
以吲哚类化合物为原料,通过一步分子间交叉偶联反应合成2位吲哚基取代的吲哚-3-酮类化合物是一种简洁、高效的合成途径。目前,实施上述反应的方法主要有两类,一类是同时使用催化量过渡金属试剂和催化量氧化剂合成得到(RSC Adv.2019,9,24050;Org.Lett.2016,18,1534;Molecules 2020,25,419);另一类是通过使用化学计量的氧化剂直接氧化合成得到(Org.Biomol.Chem.2019,17,2199;CN108218762A)。但是上述方法通常具有以下缺点,例如反应条件苛刻,化学选择性差,底物范围有限,反应的产量较低。
发明内容
1.本发明的目的是提供一种2位吲哚基取代吲哚-3-酮类化合物的合成方法,该方法通过一步分子间交叉偶联反应高效合成2位双取代的吲哚-3-酮,具有收率高、操作简便、反应条件温和、底物适用范围广等优点。
2.本发明所合成的2位吲哚基取代吲哚-3-酮类化合物,其结构通式为:
其中,R1、R4为吲哚芳环任意位置上的取代基,且为氢、烷基、卤素、烷氧基、酯基或硝基;R2为烷基或芳基;R3、R5为氢、烷基或芳基;X原子为碳(C)或氮(N)原子。
3.本发明还提供了上述2位吲哚基取代吲哚-3-酮类化合物的合成方法,采用的技术方案为:
2位吲哚基取代吲哚-3-酮的合成方法,包括如下操作:以式(I)所示的底物2-取代吲哚和式(II)所示的底物吲哚为原料,在可见光光敏剂、路易斯酸、溶剂、空气(优选氧气)以及可见光存在下,一步反应(优选室温)制得式(III)所示的2位吲哚基取代吲哚-3-酮化合物的方法;反应方程式为:
其中,R1、R4为吲哚芳环任意位置上的取代基,且为氢、烷基、卤素、烷氧基、酯基或硝基;R2为烷基或芳基;R3、R5为氢、烷基或芳基;X原子为碳(C)或氮(N)原子。
进一步地,在上述技术方案中,所述式(I)所示的底物、式(II)所示的底物、光敏剂、路易斯酸的摩尔比为:(1-2):1:(0.001-0.3):(0-1)。
进一步地,在上述技术方案中,所述反应溶剂为起到溶解原料的作用,优选为甲醇、乙腈、二氯甲烷、氯仿、硝基甲烷或硝基乙烷。
进一步地,在上述技术方案中,所述可见光光敏剂优选为钌化合物、铱化合物或有机染料。
进一步地,在上述技术方案中,所述路易斯酸优选为高氯酸镁、三氟甲磺酸锌、三氟甲磺酸铜、三氟甲磺酸亚铜、三氟甲磺酸铁、三氟甲磺酸钇、三氟甲磺酸钪或三氟甲磺酸镍。
进一步地,在上述技术方案中,反应温度为室温,反应时间1-48h。
进一步地,在上述技术方案中,反应在空气或氧气氛围下进行。
本发明优点:
本发明所述的一种2位吲哚基取代吲哚-3-酮的合成方法,使用可见光做光源,具有化学选择性好、反应条件温和、操作简单、收率高、底物适用范围广等优点。
附图说明
为了证明本发明的产物,本发明提供部分实施例的核磁氢谱图和核磁碳谱图
图1-1是实施例1的产物的核磁氢谱图。
图1-2是实施例1的产物的核磁碳谱图。
图2-1是实施例2的产物的核磁氢谱图。
图2-2是实施例2的产物的核磁碳谱图。
图3-1是实施例3的产物的核磁氢谱图。
图3-2是实施例3的产物的核磁碳谱图。
图4-1是实施例4的产物的核磁氢谱图。
图4-2是实施例4的产物的核磁碳谱图。
图5-1是实施例5的产物的核磁氢谱图。
图5-2是实施例5的产物的核磁碳谱图。
图6-1是实施例6的产物的核磁氢谱图。
图6-2是实施例6的产物的核磁碳谱图。
图7-1是实施例7的产物的核磁氢谱图。
图7-2是实施例7的产物的核磁碳谱图。
图8-1是实施例8的产物的核磁氢谱图。
图8-2是实施例8的产物的核磁碳谱图。
图9-1是实施例9的产物的核磁氢谱图。
图9-2是实施例9的产物的核磁碳谱图。
图10-1是实施例10的产物的核磁氢谱图。
图10-2是实施例10的产物的核磁碳谱图。
图11-1是实施例11的产物的核磁氢谱图。
图11-2是实施例11的产物的核磁碳谱图。
图12-1是实施例12的产物的核磁氢谱图。
图12-2是实施例12的产物的核磁碳谱图。
图13-1是实施例13的产物的核磁氢谱图。
图13-2是实施例13的产物的核磁碳谱图。
图14-1是实施例14的产物的核磁氢谱图。
图14-2是实施例14的产物的核磁碳谱图。
图15-1是实施例15的产物的核磁氢谱图。
图15-2是实施例15的产物的核磁碳谱图。
图16-1是实施例16的产物的核磁氢谱图。
图16-2是实施例16的产物的核磁碳谱图。
图17是本发明合成方法的反应方程式图。
具体实施方式
以下以具体实施例来说明本发明的合成方案,本发明的优点和特点将会随着描述而更为清楚,但这些实施例仅是范例性的,并不对本发明的范围构成任何限制。本领域技术人员应该理解的是,在不偏离本发明的精神和范围下可以对本发明技术方案的细节和形式进修修改或替换,但这些修改和替换均落入本发明的保护范围内。
实施例1以吲哚和2-苯基吲哚为底物合成2-(1H-吲哚-3-基)-2-苯基吲哚-3-酮
室温下向25mL反应器加入硝基甲烷(5mL),吲哚(50mg,0.427mmol,1.0equiv),2-苯基吲哚(98.9mg,0.512mmol,1.2equiv),氯化三(2,2'-联吡啶)钌(II)六水合物(2.4mg,0.003mmol,0.0075equiv)和三氟甲磺酸锌(15.5mg,0.043mmol,0.1equiv),在氧气氛围下,于蓝色LED光照下反应24小时。TLC显示原料反应完全后,反应液浓缩后过柱分离(石油醚:乙酸乙酯体积比=7:1)得到黄色粉末状固体2-(1H-吲哚-3-基)-2-苯基吲哚-3-酮103.7mg,收率为75%。熔点:72.6–77.7℃;1H NMR(400MHz,DMSO-d6)δ11.08(s,1H),8.33(s,1H),7.53–7.43(m,4H),7.39–7.26(m,4H),7.09–7.02(m,3H),6.97(d,J=8.4Hz,1H),6.84(t,J=8.0Hz,1H),6.73(t,J=7.6Hz,1H);13C NMR(100MHz,DMSO)δ200.3,160.9,140.0,137.8,136.9,128.2,127.4,126.6,125.5,124.6,124.1,121.4,120.0,118.6,117.5,117.4,114.5,112.0,111.8,70.6。
实施例2以吲哚和2-甲基吲哚为底物合成2-(1H-吲哚-3-基)-2-甲基吲哚-3-酮
室温下向25mL反应器加入硝基甲烷(5mL),吲哚(50mg,0.427mmol,1.0equiv),2-甲基吲哚(84.0mg,0.640mmol,1.5equiv),氯化三(2,2'-联吡啶)钌(II)六水合物(2.4mg,0.003mmol,0.0075equiv)和三氟甲磺酸锌(15.5mg,0.043mmol,0.1equiv),在氧气氛围下,于蓝色LED光照下反应24小时。TLC显示原料反应完全后,反应液浓缩后过柱分离(石油醚:乙酸乙酯体积比=7:1)得到黄色粉末状固体2-(1H-吲哚-3-基)-2-甲基吲哚-3-酮90.0mg,收率为81%。熔点:184.3–188.0℃;1H NMR(400MHz,DMSO-d6)δ11.04(s,1H),7.75(s,1H),7.51(t,J=7.6Hz,1H),7.46(d,J=8.0Hz,1H),7.39(d,J=2.4Hz,1H),7.34(d,J=8.0Hz,1H),7.13(d,J=8.0Hz,1H),7.03(t,J=7.6Hz,1H),6.92(d,J=8.4Hz,1H),6.83(t,J=7.6Hz,1H),6.73(t,J=7.2Hz,1H),1.65(s,3H);13C NMR(100MHz,DMSO-d6)δ203.3,160.6,137.6,136.7,124.9,124.4,123.5,121.1,119.6,118.5,117.9,117.1,114.5,111.9,111.6,65.1,23.3。
实施例3以吲哚-5-甲腈和2-苯基吲哚为底物合成2-(1H-吲哚-5-氰基-3-基)-2-苯基吲哚-3-酮
室温下向25mL反应器加入硝基甲烷(5mL),吲哚-5-甲腈(50mg,0.352mmol,1.0equiv),2-苯基吲哚(81.6mg,0.422mmol,1.2equiv),氯化三(2,2'-联吡啶)钌(II)六水合物(2.0mg,0.003mmol,0.0075equiv)和三氟甲磺酸锌(12.8mg,0.035mmol,0.1equiv),在氧气氛围下,于蓝色LED光照下反应24小时。TLC显示原料反应完全后,反应液浓缩后过柱分离(石油醚:乙酸乙酯体积比=7:1)得到黄色粉末状固体2-(1H-吲哚-5-氰基-3-基)-2-苯基吲哚-3-酮94.9mg,收率为77%。熔点:67.6–71.1℃;1H NMR(600MHz,DMSO-d6)δ11.70(s,1H),8.50(s,1H),7.58(s,1H),7.57(d,J=8.4Hz,1H),7.54(td,J=6.6,1.2Hz,1H),7.49(d,J=7.8Hz,1H),7.43(dd,J=8.4,1.8Hz,1H),7.40(s,1H),7.38–7.28(m,5H),6.99(d,J=8.4Hz,1H),6.77(t,J=7.2Hz,1H);13C NMR(150MHz,DMSO-d6)δ199.8,160.9,139.7,138.8,138.1,128.4,127.7,126.5,126.4,125.6,125.3,124.8,124.0,120.6,117.9,117.1,115.3,113.3,111.9,100.8,70.3。
实施例4以5-氟吲哚和2-苯基吲哚为底物合成2-(1H-吲哚-5-氟-3-基)-2-苯基吲哚-3-酮
室温下向25mL反应器加入硝基甲烷(5mL),5-氟吲哚(50mg,0.370mmol,1.0equiv),2-苯基吲哚(85.8mg,0.444mmol,1.2equiv),氯化三(2,2'-联吡啶)钌(II)六水合物(2.0mg,0.003mmol,0.0075equiv)和三氟甲磺酸锌(13.5mg,0.037mmol,0.1equiv),在氧气氛围下,于蓝色LED光照下反应24小时。TLC显示原料反应完全后,反应液浓缩后过柱分离(石油醚:乙酸乙酯体积比=7:1)得到黄色粉末状固体2-(1H-吲哚-5-氟-3-基)-2-苯基吲哚-3-酮94.8mg,收率为75%。熔点:219.3–219.6℃;1H NMR(600MHz,CDCl3)δ8.28(s,1H),7.67(d,J=7.8Hz,1H),7.54–7.48(m,3H),7.33–7.22(m,4H),7.16(d,J=2.4Hz,1H),6.94(d,J=8.4Hz,1H),6.92–6.86(m,2H),6.78(dd,J=9.6,3.0Hz,1H),5.33(s,1H);13C NMR(150MHz,CDCl3)δ200.5,160.4,158.5/156.9(d,JCF=234.3Hz),139.2,137.7,133.4,128.5,127.9,126.7,126.0/125.9(d,JCF=10.0Hz),125.6,125.5,119.8,119.5,115.8/115.8(d,JCF=3.6Hz),112.9,112.3/112.3(d,JCF=9.7Hz),111.1/110.9(d,JCF=26.2Hz),105.0/104.8(d,JCF=23.8Hz),71.1。
实施例5以6-氯吲哚和2-苯基吲哚为底物合成2-(1H-吲哚-6-氯-3-基)-2-苯基吲哚-3-酮
室温下向25mL反应器加入硝基甲烷(5mL),6-氯吲哚(50mg,0.330mmol,1.0equiv),2-苯基吲哚(76.5mg,0.396mmol,1.2equiv),氯化三(2,2'-联吡啶)钌(II)六水合物(2.0mg,0.003mmol,0.0075equiv)和三氟甲磺酸锌(12.0mg,0.033mmol,0.1equiv),在氧气氛围下,于蓝色LED光照下反应24小时。TLC显示原料反应完全后,反应液浓缩后过柱分离(石油醚:乙酸乙酯体积比=7:1)得到黄色粉末状固体2-(1H-吲哚-6-氯-3-基)-2-苯基吲哚-3-酮96.0mg,收率为81%。熔点:208.0–208.8℃;1H NMR(600MHz,CDCl3)δ8.27(s,1H),7.67(d,J=7.2Hz,1H),7.53–7.48(m,3H),7.33(d,J=1.8Hz,1H),7.31–7.24(m,3H),7.11(d,J=2.4Hz,1H),7.03(d,J=9.0Hz,1H),6.95–6.91(m,2H),6.89(t,J=7.2Hz,1H),5.31(s,1H);13C NMR(150MHz,CDCl3)δ200.7,160.6,139.5,137.9,137.5,128.7,128.7,128.1,126.9,125.8,124.6,124.4,120.9,120.0,119.7,116.1,113.0,111.7,71.3。
实施例6以5-溴吲哚和2-苯基吲哚为底物合成2-(1H-吲哚-5-溴-3-基)-2-苯基吲哚-3-酮
室温下向25mL反应器加入硝基甲烷(5mL),5-溴吲哚(50mg,0.255mmol,1.0equiv),2-苯基吲哚(59.1mg,0.306mmol,1.2equiv),氯化三(2,2'-联吡啶)钌(II)六水合物(1.4mg,0.003mmol,0.0075equiv)和三氟甲磺酸锌(9.2mg,0.025mmol,0.1equiv),在氧气氛围下,于蓝色LED光照下反应24小时。TLC显示原料反应完全后,反应液浓缩后过柱分离(石油醚:乙酸乙酯体积比=7:1)得到黄色粉末状固体2-(1H-吲哚-5-溴-3-基)-2-苯基吲哚-3-酮64mg,收率为62%。熔点:78.9–85.1℃;1H NMR(600MHz,DMSO-d6)δ11.31(s,1H),8.43(s,1H),7.52(td,J=7.2,1.2Hz,1H),7.48(d,J=7.8Hz,1H),7.40–7.27(m,6H),7.27(d,J=1.8Hz,1H)7.19(d,J=2.4Hz,1H),7.17(dd,J=8.4,1.8Hz,1H),6.98(d,J=8.4Hz,1H),6.75(t,J=7.2Hz,1H);13C NMR(150MHz,DMSO-d6)δ200.0,160.9,139.8,137.9,135.6,128.3,127.6,127.3,126.5,125.6,124.7,123.9,122.2,117.6,117.2,114.0,113.8,111.9,111.4,70.4。
实施例7以5-氯-7-氮杂吲哚和2-苯基吲哚为底物合成2-(1H-吲哚-5-氯-7-氮杂-3-基)-2-苯基吲哚-3-酮
室温下向25mL反应器加入硝基甲烷(5mL),5-氯-7-氮杂吲哚(50mg,0.328mmol,1.0equiv),2-苯基吲哚(76.2mg,0.394mmol,1.2equiv),氯化三(2,2'-联吡啶)钌(II)六水合物(1.8mg,0.003mmol,0.0075equiv)和三氟甲磺酸锌(12mg,0.033mmol,0.1equiv),在氧气氛围下,于蓝色LED光照下反应24小时。TLC显示原料反应完全后,反应液浓缩后过柱分离(石油醚:乙酸乙酯体积比=7:1)得到黄色粉末状固体2-(1H-吲哚-5-氯-7-氮杂-3-基)-2-苯基吲哚-3-酮68.8mg,收率为58%。熔点:248.0–248.3℃;1H NMR(600MHz,CDCl3)δ9.57(s,1H),8.21(d,J=1.8Hz,1H),7.69(d,J=6.6Hz,1H),7.53(t,J=8.4Hz,1H),7.52(d,J=1.8Hz,1H),7.48–7.45(m,2H),7.39(d,J=2.4Hz,1H),7.33(m,3H),7.26(s,1H),6.97(d,J=7.2Hz,1H),6.92(d,J=6.6Hz,1H),5.22(s,1H);13C NMR(150MHz,CDCl3)δ200.4,160.3,147.5,142.4,139.4,138.0,129.0,128.5,126.9,125.8,125.7,124.3,120.2,119.8,119.3,114.7,113.0,71.8。
实施例8以5-氯吲哚和2-苯基吲哚为底物合成2-(1H-吲哚-5-氯-3-基)-2-苯基吲哚-3-酮
室温下向25mL反应器加入硝基甲烷(5mL),5-氯吲哚(50mg,0.330mmol,1.0equiv),2-苯基吲哚(76.5mg,0.396mmol,1.2equiv),氯化三(2,2'-联吡啶)钌(II)六水合物(1.8mg,0.003mmol,0.0075equiv)和三氟甲磺酸锌(12mg,0.033mmol,0.1equiv),在氧气氛围下,于蓝色LED光照下反应24小时。TLC显示原料反应完全后,反应液浓缩后过柱分离(石油醚:乙酸乙酯体积比=7:1)得到黄色粉末状固体2-(1H-吲哚-5-氯-3-基)-2-苯基吲哚-3-酮97.7mg,收率为83%。熔点:188.8–189.5℃;1H NMR(600MHz,DMSO-d6)δ11.31(s,1H),8.43(s,1H),7.52(td,J=7.2 0.6Hz,1H),7.48(d,J=7.8Hz,1H),7.43–7.38(m,3H),7.35–7.27(m,3H),7.22(d,J=2.4Hz,1H),7.13(d,J=1.8Hz,1H),7.07(dd,J=9.0,2.4Hz,1H),6.99(d,J=8.4Hz,1H),6.75(t,J=7.2Hz,1H);13C NMR(150MHz,DMSO-d6)δ200.0,160.9,139.8,137.9,135.4,128.3,127.6,126.6,126.5,125.7,124.7,123.3,121.4,119.2,117.7,117.2,114.2,113.4,111.9,70.4。
实施例9以吲哚-5-甲酸甲酯和2-苯基吲哚为底物合成2-(1H-吲哚-5-甲酸甲酯-3-基)-2-苯基吲哚-3-酮
室温下向25mL反应器加入硝基甲烷(5mL),吲哚-5-甲酸甲酯(50mg,0.285mmol,1.0equiv),2-苯基吲哚(66.2mg,0.343mmol,1.2equiv),氯化三(2,2'-联吡啶)钌(II)六水合物(1.6mg,0.002mmol,0.0075equiv)和三氟甲磺酸锌(10.4mg,0.029mmol,0.1equiv),在氧气氛围下,于蓝色LED光照下反应24小时。TLC显示原料反应完全后,反应液浓缩后过柱分离(石油醚:乙酸乙酯体积比=7:1)得到黄色粉末状固体2-(1H-吲哚-5-甲酸甲酯-3-基)-2-苯基吲哚-3-酮98.2mg,收率为90%。熔点:109.4–113.6℃;1H NMR(600MHz,DMSO-d6)δ11.50(s,1H),8.43(s,1H),7.90(s,1H),7.72–7.69(m,1H),7.55–7.45(m,3H),7.43–7.40(m,2H),7.35–7.27(m,3H),7.24(m,1H),7.00(d,J=8.4Hz,1H),6.76(t,J=7.2Hz,1H),3.74(s,3H);13C NMR(150MHz,DMSO-d6)δ200.1,167.1,161.1,139.9,139.6,137.9,128.3,127.6,126.6,125.9,125.1,124.7,123.0,122.4,120.3,117.7,117.3,115.9,112.1,111.7,70.5,51.6。
实施例10以吲哚-5-羧酸和2-苯基吲哚为底物合成2-(1H-吲哚-5-羧酸-3-基)-2-苯基吲哚-3-酮
室温下向25mL反应器加入硝基甲烷(5mL),吲哚-5-羧酸(50mg,0.310mmol,1.0equiv),2-苯基吲哚(71.9mg,0.372mmol,1.2equiv),氯化三(2,2'-联吡啶)钌(II)六水合物(1.7mg,0.002mmol,0.0075equiv)和三氟甲磺酸锌(11.3mg,0.031mmol,0.1equiv),在氧气氛围下,于蓝色LED光照下反应24小时。TLC显示原料反应完全后,反应液浓缩后过柱分离(石油醚:乙酸乙酯体积比=7:1)得到黄色粉末状固体2-(1H-吲哚-5-羧酸-3-基)-2-苯基吲哚-3-酮56.8mg,收率为50%。熔点:239.4–241.1℃;1H NMR(600MHz,DMSO-d6)δ12.26(s,1H),11.43(d,J=2.4Hz,1H),8.41(s,1H),7.87(s,1H),7.69(dd,J=8.4,1.2Hz,1H),7.54–7.46(m,2H),7.45–7.40(m,3H),7.34–7.27(m,3H),7.20(d,J=2.4Hz,1H),6.99(d,J=8.4Hz,1H),6.77–6.73(m,1H);13C NMR(150MHz,DMSO-d6)δ200.1,168.2,161.0,139.9,139.5,137.8,128.3,127.6,126.6,125.7,125.1,124.7,123.1,122.7,121.3,117.7,117.2,115.7,112.1,111.5,70.5。
实施例11以5-甲氧基吲哚和2-甲基吲哚为底物合成2-(1H-吲哚-5-甲氧基-3-基)-2-甲基吲哚-3-酮
室温下向25mL反应器加入硝基甲烷(5mL),5-甲氧基吲哚(50mg,0.340mmol,1.0equiv),2-甲基吲哚(66.9mg,0.510mmol,1.5equiv),氯化三(2,2'-联吡啶)钌(II)六水合物(1.9mg,0.003mmol,0.0075equiv)和三氟甲磺酸锌(12.4mg,0.034mmol,0.1equiv),在氧气氛围下,于蓝色LED光照下反应24小时。TLC显示原料反应完全后,反应液浓缩后过柱分离(石油醚:乙酸乙酯体积比=7:1)得到黄色粉末状固体2-(1H-吲哚-5-甲氧基-3-基)-2-甲基吲哚-3-酮63.6mg,收率为64%。熔点:194.9–195.7℃;1H NMR(600MHz,DMSO-d6)10.86(s,1H),7.73(s,1H),7.52(td,J=7.2,1.2Hz,1H),7.47(d,J=7.8Hz,1H),7.33(d,J=2.4Hz,1H),7.23(d,J=9.0Hz,1H),6.92(d,J=8.4Hz,1H),6.73(t,J=6.6Hz,1H),6.68(dd,J=9.0,3.0Hz,1H),6.59(d,J=2.4Hz,1H),3.48(s,3H),1.63(s,3H);13C NMR(150MHz,DMSO-d6)δ203.3,160.7,152.8,137.5,131.9,125.1,124.3,124.1,118.1,117.0,114.2,112.1,111.8,110.8,101.9,65.1,54.8,22.9。
实施例12以吲哚-5-甲腈和2-甲基吲哚为底物合成2-(1H-吲哚-5-甲腈-3-基)-2-甲基吲哚-3-酮
室温下向25mL反应器加入硝基甲烷(5mL),吲哚-5-甲腈(50mg,0.352mmol,1.0equiv),2-甲基吲哚(69.2mg,0.528mmol,1.5equiv),氯化三(2,2'-联吡啶)钌(II)六水合物(2.0mg,0.003mmol,0.0075equiv)和三氟甲磺酸锌(12.8mg,0.035mmol,0.1equiv),在氧气氛围下,于蓝色LED光照下反应24小时。TLC显示原料反应完全后,反应液浓缩后过柱分离(石油醚:乙酸乙酯体积比=7:1)得到黄色粉末状固体2-(1H-吲哚-5-甲腈-3-基)-2-甲基吲哚-3-酮81.1mg,收率为80%。熔点:237.8–238.0℃;1H NMR(600MHz,DMSO-d6)δ11.66(s,1H),7.86(s,1H),7.71(d,J=1.2Hz,1H),7.60(s,1H),7.55(td,J=7.2,1.2Hz,1H),7.53(d,J=7.8Hz,1H),7.48(d,J=6.6Hz,1H),7.41(dd,J=8.4,1.8Hz,1H),6.97(d,J=8.4Hz,1H),6.77(t,J=7.8Hz,1H),1.66(s,3H);13C NMR(150MHz,DMSO-d6)δ202.7,160.6,138.6,137.9,126.0,125.2,124.6,124.6,123.8,120.7,117.6,117.5,115.8,113.1,112.1,100.7,65.0,23.6。
实施例13以5-氟吲哚和2-甲基吲哚为底物合成2-(1H-吲哚-5-氟-3-基)-2-甲基吲哚-3-酮
室温下向25mL反应器加入硝基甲烷(5mL),5-氟吲哚(50mg,0.370mmol,1.0equiv),2-甲基吲哚(72.8mg,0.555mmol,1.5equiv),氯化三(2,2'-联吡啶)钌(II)六水合物(2.0mg,0.003mmol,0.0075equiv)和三氟甲磺酸锌(13.5mg,0.037mmol,0.1equiv),在氧气氛围下,于蓝色LED光照下反应24小时。TLC显示原料反应完全后,反应液浓缩后过柱分离(石油醚:乙酸乙酯体积比=7:1)得到黄色粉末状固体2-(1H-吲哚-5-氟-3-基)-2-甲基吲哚-3-酮79.0mg,收率为76%。熔点:212.4–213.0℃;1H NMR(600MHz,DMSO-d6)δ11.16(s,1H),7.76(s,1H),7.53(td,J=6.6,1.2Hz,1H),7.46(q,J=3.0Hz,2H),7.34(dd,J=9.0,4.8Hz,1H),6.93(d,J=8.4Hz,1H),6.88(td,J=9.0,2.4Hz,1H),6.83(dd,J=10.8,2.4Hz,1H),6.74(t,J=7.2Hz,1H),1.62(s,3H);13C NMR(150MHz,DMSO-d6)δ203.1,160.6,157.2/155.7(d,JCF=229.5Hz),137.7,133.4,125.5,124.9/124.9(d,JCF=9.9Hz),124.4,117.8,117.3,114.8/114.8(d,JCF=4.4Hz),112.7/112.6(d,JCF=9.7Hz),112.0,109.4/109.2(d,JCF=25.9Hz),104.3/104.1(d,JCF=23.7Hz),65.0,23.3。
实施例14以6-氯吲哚和2-甲基吲哚为底物合成2-(1H-吲哚-6-氯-3-基)-2-甲基吲哚-3-酮
室温下向25mL反应器加入硝基甲烷(5mL),6-氯吲哚(50mg,0.330mmol,1.0equiv),2-甲基吲哚(64.9mg,0.495mmol,1.5equiv),氯化三(2,2'-联吡啶)钌(II)六水合物(1.9mg,0.003mmol,0.0075equiv)和三氟甲磺酸锌(12.0mg,0.033mmol,0.1equiv),在氧气氛围下,于蓝色LED光照下反应24小时。TLC显示原料反应完全后,反应液浓缩后过柱分离(石油醚:乙酸乙酯体积比=7:1)得到黄色粉末状固体2-(1H-吲哚-6-氯-3-基)-2-甲基吲哚-3-酮75.6mg,收率为77%。熔点:59.0–61.0℃;1H NMR(600MHz,DMSO-d6)δ11.18(s,1H),7.76(s,1H),7.51(td,J=7.2,1.2Hz,1H),7.46(d,J=7.8Hz,1H),7.42(d,J=1.8Hz,1H),7.39(d,J=1.8Hz,1H),7.16(d,J=8.4Hz,1H),6.92(d,J=8.4Hz,1H),6.88(dd,J=8.4,1.8Hz,1H),6.74(d,J=7.8Hz,1H),1.63(s,3H);13C NMR(150MHz,DMSO-d6)δ203.0,160.6,137.6,137.2,125.9,124.6,124.4,123.7,120.9,118.9,117.7,117.3,114.9,112.0,111.2,65.0,23.3。
实施例15以5-甲氧基吲哚和2-苯基吲哚为底物合成2-(1H-吲哚-5-甲氧基-3-基)-2-苯基吲哚-3-酮
室温下向25mL反应器加入硝基甲烷(5mL),5-甲氧基吲哚(50mg,0.340mmol,1.0equiv),2-苯基吲哚(78.8mg,0.408mmol,1.2equiv),氯化三(2,2'-联吡啶)钌(II)六水合物(1.9mg,0.003mmol,0.0075equiv)和三氟甲磺酸锌(12.4mg,0.034mmol,0.1equiv),在氧气氛围下,于蓝色LED光照下反应24小时。TLC显示原料反应完全后,反应液浓缩后过柱分离(石油醚:乙酸乙酯体积比=7:1)得到黄色粉末状固体2-(1H-吲哚-5-甲氧基-3-基)-2-苯基吲哚-3-酮73.4mg,收率为61%。熔点:88.9–92.0℃;1H NMR(400MHz,DMSO-d6)δ10.93(s,1H),8.36/5.96(s,1H),7.54–7.47(m,4H),7.36–7.26(m,4H),7.03–6.96(m,2H),6.77–6.70(m,2H),6.55(d,J=2.4Hz,1H),3.52(s,3H);13C NMR(100MHz,DMSO-d6)δ200.4,161.0,152.8,139.9,137.8,132.1,128.1,127.4,126.7,125.9,124.8,124.6,117.5,117.5,114.2,112.3,111.9,110.9,102.5,70.6,55.1。
实施例16以吲哚和2-乙基吲哚为底物合成2-(1H-吲哚-3-基)-2-乙基吲哚-3-酮
室温下向25mL反应器加入硝基甲烷(5mL),吲哚(50mg,0.427mmol,1.0equiv),2-乙基吲哚(74.4mg,0.512mmol,1.2equiv),氯化三(2,2'-联吡啶)钌(II)六水合物(2.4mg,0.003mmol,0.0075equiv)和三氟甲磺酸锌(15.5mg,0.043mmol,0.1equiv),在氧气氛围下,于蓝色LED光照下反应24小时。TLC显示原料反应完全后,反应液浓缩后过柱分离(石油醚:乙酸乙酯体积比=7:1)得到黄色粉末状固体2-(1H-吲哚-3-基)-2-乙基吲哚-3-酮74.7mg,收率为63%。熔点:142.7–145.2℃;1H NMR(600MHz,DMSO-d6)δ11.02(s,1H),7.77(s,1H),7.48(t,J=7.2Hz,1H),7.41(dd,J=13.2,8.4Hz,2H),7.37–7.28(m,2H),7.03(t,J=7.2Hz,1H),6.95(d,J=8.4Hz,1H),6.86(t,J=7.2Hz,1H),6.69(t,J=7.2Hz,1H),2.20(dq,J=14.4,7.2Hz,1H),2.09(dq,J=13.8,6.6Hz,1H),0.79(t,J=6.6Hz,3H);13C NMR(150MHz,DMSO-d6)δ202.8,161.4,137.4,136.8,125.0,124.0,123.2,121.1,120.1,118.9,118.5,116.9,113.6,111.7,111.6,69.2,29.4,8.1。
Claims (7)
1.一种2位吲哚基取代吲哚-3-酮化合物的合成方法,其特征在于以式(I)所示的底物2-取代吲哚和式(II)所示的底物吲哚为原料,在可见光光敏剂、路易斯酸、溶剂、空气以及可见光存在下,一步反应制得式(III)所示的2位吲哚基取代吲哚-3-酮化合物的方法;
;
其中,R1、R4为吲哚芳环任意位置上的取代基,且为氢、烷基、卤素、烷氧基、酯基或硝基;R2为烷基或芳基;R3、R5为氢、烷基或芳基;X原子为碳(C)或氮(N)原子。
2.根据权利要求1所述的2位吲哚基取代吲哚-3-酮类化合物的合成方法,其特征在于式(II)所示的底物、可见光光敏剂与路易斯酸的摩尔比为1 : (0.001-0.3) : (0-1)。
3.根据权利要求1所述的2位吲哚基取代吲哚-3-酮类化合物的合成方法,其特征在于所述底物式(I)2-取代吲哚与式(II)吲哚的投料质量比为1-2:1。
4.根据权利要求1所述的2位吲哚基取代吲哚-3-酮类化合物的合成方法,其特征在于所述可见光光敏剂选自钌化合物、铱化合物、有机染料中的至少一种。
5.根据权利要求1所述的2位吲哚基取代吲哚-3-酮类化合物的合成方法,其特征在于路易斯酸选自高氯酸镁、三氟甲磺酸锌、三氟甲磺酸铜、三氟甲磺酸亚铜、三氟甲磺酸铁、三氟甲磺酸钇、三氟甲磺酸钪、三氟甲磺酸镍中的一种或几种任意比例的混合物。
6.根据权利要求1所述的2位吲哚基取代吲哚-3-酮类化合物的合成方法,其特征在于溶剂选自甲醇、乙腈、二氯甲烷、氯仿、硝基甲烷、硝基乙烷中的一种或几种任意比例的混合物。
7.根据权利要求1所述的2位吲哚基取代吲哚-3-酮类化合物的合成方法,其特征在于所述一步反应的条件包括:温度为0-80 ºC,时间为1-48 h,可见光光源为白光或蓝光。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310682289.9A CN116751150A (zh) | 2023-06-09 | 2023-06-09 | 一种2位吲哚基取代吲哚-3-酮类化合物的合成方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310682289.9A CN116751150A (zh) | 2023-06-09 | 2023-06-09 | 一种2位吲哚基取代吲哚-3-酮类化合物的合成方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN116751150A true CN116751150A (zh) | 2023-09-15 |
Family
ID=87954634
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310682289.9A Pending CN116751150A (zh) | 2023-06-09 | 2023-06-09 | 一种2位吲哚基取代吲哚-3-酮类化合物的合成方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116751150A (zh) |
-
2023
- 2023-06-09 CN CN202310682289.9A patent/CN116751150A/zh active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113880750B (zh) | 一种手性3-取代-3-芳基氧化吲哚类化合物的合成方法 | |
CN111675712B (zh) | 一种吡唑啉酮并苯二氮杂卓类化合物的合成方法 | |
CN108299296B (zh) | 一种菲啶类杂环化合物的制备方法 | |
CN112480050B (zh) | 一种富勒烯并螺环衍生物的合成方法 | |
CN106674083A (zh) | 一种光电材料中间体9‑(4′‑氯联苯‑2‑基)咔唑的合成方法 | |
CN110878099B (zh) | 一种吡咯[1,2,α]吲哚生物碱衍生物的制备方法 | |
CN110483421B (zh) | 一种喹喔啉酮衍生物的制备方法 | |
CN111285881B (zh) | 一种噻吩并[3,4-b]吲哚衍生物及其合成方法 | |
CN109651385B (zh) | 一种吡喃[3,2-a]咔唑类化合物的制备方法 | |
CN109734703B (zh) | 一种吲哚啉-7-羧酸酯类化合物的制备方法 | |
CN114835652B (zh) | 一种光催化条件下合成亚胺基苯并三唑类化合物的方法 | |
CN109879792B (zh) | 一种多取代异吲哚类化合物及其制备方法 | |
CN109293550B (zh) | 一种含三氟甲基3,6’-非对称双吲哚化合物及其合成方法 | |
CN116751150A (zh) | 一种2位吲哚基取代吲哚-3-酮类化合物的合成方法 | |
CN107382910B (zh) | 一种二氟甲基化醛腙类化合物及其制备方法 | |
CN113912609B (zh) | 一种天然生物碱色胺酮及其衍生物的制备方法 | |
CN113045496B (zh) | 选择性合成二氢菲啶或菲啶类化合物的方法 | |
CN114014865A (zh) | 一种不对称三聚吲哚化合物及其制备方法 | |
CN108640914B (zh) | 一种合成异吲哚[2,1-b]异喹啉-5,7-二酮类化合物的方法 | |
CN108218762B (zh) | 一种2位季碳吲哚-3-酮类化合物的合成方法 | |
CN111285846B (zh) | 一种2-(2-吲哚基)-乙酸酯衍生物及其合成方法 | |
CN114920684B (zh) | 含硒苯甲酰胺类化合物及其合成方法与应用 | |
CN115490628B (zh) | 一种二氟乙醇类化合物的制备方法 | |
CN110117246B (zh) | 一种3-位吲哚化环己烯酮化合物的制备方法 | |
CN112209866B (zh) | 一种制备1-叔丁基-3,3-二甲基吲哚啉类化合物的方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |